US8664370B2 - Process for preparing silicon-containing azodicarbamides - Google Patents

Process for preparing silicon-containing azodicarbamides Download PDF

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Publication number
US8664370B2
US8664370B2 US13/580,780 US201113580780A US8664370B2 US 8664370 B2 US8664370 B2 US 8664370B2 US 201113580780 A US201113580780 A US 201113580780A US 8664370 B2 US8664370 B2 US 8664370B2
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aminopropyl
general formula
producing silicon
reaction
dicarbamides
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US20130012691A1 (en
Inventor
Karsten Korth
Julia Keck
Susann Witzsche
Oliver Klockmann
Jaroslaw Monkiewicz
Christian Springer
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage

Definitions

  • the invention relates to a process for producing silicon-containing azodicarbamides.
  • DE 2704506 discloses compounds of the general formula Y—X—CO—N ⁇ N—CO—X 1 —Z and use thereof in filled rubber mixtures.
  • US 20090234066 A1 moreover discloses compounds of the A-CO—N ⁇ N—CO—Z-G type, which are used together with sulphur-containing silanes in rubber mixtures comprising isoprene rubber.
  • US 20090186961 A1 discloses compounds of the A-CO—N ⁇ N—CO—Z-G type, which are used together with coating materials in rubber mixtures comprising isoprene rubber.
  • the invention provides a process for producing silicon-containing azodicarbamides of the general formula I (R 1 ) 3-a (R 2 ) a Si—R I —NH—C(O)—N ⁇ N—C(O)—NH—R I —Si(R 1 ) 3-a (R 2 ) a (I), via reaction of azobiscarboxy compounds of the general formula II R 3 —X 1 —C(O)—N ⁇ N—C(O)—X 1 —R 4 (II) with aminosilanes of the general formula III (R 1 ) 3-a (R 2 ) a Si—R I —NH 2 (III),
  • Silicon-containing azobiscarbamides can be mixtures of silicon-containing azobiscarbamides of the general formula I.
  • the product of the process can comprise oligomers produced via hydrolysis and condensation of the alkoxysilane functions of the silicon-containing azobiscarbamides of the general formula I.
  • the azobiscarboxy compound used as starting material can be a mixture of azobiscarboxy compounds of the general formula II.
  • the aminosilane used as starting material can be a mixture of aminosilanes of the general formula III.
  • the aminosilanes used can comprise oligomers produced via hydrolysis and condensation of the alkoxysilane functions of the aminosilanes of the general formula III.
  • the product obtainable via the process according to the invention can comprise silicon-containing azobis-carbamides of the general formula I in a purity greater than 30 mol %, preferably greater than 50 mol %, particularly preferably greater than 75 mol %, very particularly preferably greater than 85 mol %.
  • the relative percentage contents of the compounds of the general formula I in the product obtained via the process according to the invention are determined via integration of the 13 C NMR integrals of the target product of the general formula I and comparison with the totality of the 13 C NMR integrals.
  • the reaction can be carried out in solvents or with no solvent.
  • the amount of solvent as a ratio to the amounts used of the compounds of the general formula II, can be from 1% by weight to 5000% by weight, preferably from 1% by weight to 1000% by weight, particularly preferably from 50% by weight to 1000% by weight, particularly preferably from 50% by weight to 500% by weight.
  • the amount of solvent as a ratio to the amounts used of the compounds of the general formula II, can be more than 1% by weight, preferably more than 10% by weight, particularly preferably more than 50% by weight and very particularly preferably more than 100% by weight.
  • the boiling point of the solvent can be from ⁇ 100° C. to 250° C., preferably from 0 to 150° C., particularly preferably from 20 to 100° C.
  • Solvents used can comprise an alcoholic or non-alcoholic compound.
  • Solvents used can comprise mixtures of alcoholic and non-alcoholic compounds.
  • Non-alcoholic solvents can be halogen-containing or halogen-free solvents.
  • Halogen-containing solvents can preferably be CCl 4 , CHCl 3 , CH 2 Cl 2 , CH 3 Cl, CCl 3 —CCl 3 , CHCl 2 —CCl 3 , CHCl 2 —CHCl 2 or CH 2 Cl—CH 2 Cl.
  • Non-alcoholic, halogen-free solvents used can comprise alkanes, alkyl carbonates, aromatics, substituted aromatics, preferably alkyl-substituted aromatics, particularly preferably toluene, p-xylene, m-xylene or o-xylene, ethers, mercaptans, dialkyl sulphides, trialkylamines, alkylphosphanes or arylphosphanes.
  • Alkanes used can preferably comprise pure alkanes or a mixture of alkanes, examples being pentane, hexane, cyclohexane, heptane or octane.
  • Alkyl carbonates used can comprise open-chain or cyclic carbonates.
  • Open-chain alkyl carbonates used can preferably comprise dimethyl carbonate, diisopropyl carbonate or diethyl carbonate.
  • Cyclic alkyl carbonates used can preferably comprise ethylene carbonate, 1-methylethylene carbonate, propylene carbonate or glycerol carbonate.
  • Alcoholic solvents used can comprise straight-chain, branched or else cyclic alcohols.
  • Alcohols used can also comprise mixtures of alcohols.
  • alcohols which correspond to the respective alkoxy substituents on the silicon in the compounds of the formulae I and III, and also isopropanol and tert-butanol.
  • Alcoholic solvent used can very particularly preferably comprise methanol, ethanol and isopropanol.
  • the reaction can preferably be carried out with exclusion of air and/or with exclusion of water.
  • the reaction can be carried out under an inert gas atmosphere, for example under argon or nitrogen, preferably under nitrogen.
  • the process according to the invention can be carried out at atmospheric pressure, at elevated pressure or at reduced pressure.
  • Preference is given to atmospheric pressure and to reduced pressure.
  • Elevated pressure can be a pressure of from 1.1 bar to 100 bar, preferably from 1.5 bar to 50 bar, particularly preferably from 2 bar to 20 bar and very particularly preferably from 2 bar to 10 bar.
  • Reduced pressure can be a pressure from 1 mbar to 1000 mbar, preferably from 1 mbar to 500 mbar, particularly preferably from 1 mbar to 250 mbar, very particularly preferably from 5 mbar to 100 mbar.
  • the process according to the invention can be carried out at from ⁇ 50° C. to +200° C., preferably from ⁇ 25° C. to 150° C., particularly preferably from ⁇ 10° C. to 100° C., very particularly preferably from ⁇ 10° C. to 50° C.
  • the azobiscarboxy compounds of the general formula II can be added to aminosilanes of the general formula III in a molar ratio of from 1:1.80 to 1:2.25, preferably from 1:1.90 to 1:2.15, and particularly preferably in a ratio of from 1:1.95 to 1:2.05.
  • stabilizers can be added prior to, during or after the reaction.
  • Stabilizers can be monomers, oligomers or polymers.
  • Stabilizers can inhibit or delay the thermal decomposition of azo compounds.
  • Stabilizers can be free-radical scavengers.
  • Stabilizers can inhibit or delay the light-induced decomposition of azo compounds.
  • Stabilizers can be UV stabilizers.
  • Stabilizers can inhibit or delay oxidation reactions.
  • Stabilizers can be anionic or cationic compounds.
  • Stabilizers can comprise heteroatoms, such as oxygen, sulphur, nitrogen or phosphorus.
  • the amount of stabilizers that can be used in the process according to the invention is from 0.001 to 100% by weight, preferably from 0.01 to 50% by weight, particularly preferably from 0.01 to 10% by weight, very particularly preferably from 0.1 to 5% by weight, based on the mass of the material used of the general formula II.
  • the amount of stabilizers used in the process according to the invention can be more than 0.001% by weight, preferably more than 0.01% by weight, particularly preferably more than 0.1% by weight, very particularly preferably more than 1% by weight, based on the mass of the material used of the general formula II.
  • the amount of stabilizers used in the process according to the invention can be less than 100% by weight, preferably less than 25% by weight, particularly preferably less than 10% by weight, but very particularly preferably more than 1% by weight, based on the mass of the material used of the general formula II.
  • the residual content of compounds of the general formula II in the product produced by the process according to the invention can be less than 25 mol %, preferably less than 10 mol %, particularly preferably less than 5 mol %, very particularly preferably less than 3 mol %.
  • the relative mol % values for the compounds of the general formula II in the product produced by the process according to the invention are determined via integration of the carbonyl C atoms in the 13 C NMR, with respect to the mol % values for the compounds of the general formula I.
  • the residual content of compounds of the general formula III in the product produced by the process according to the invention can be less than 25 mol %, preferably less than 10 mol %, particularly preferably less than 5 mol %, very particularly preferably less than 3 mol %.
  • Relative mol % values for compounds of the formula III (integral of all of the C atoms of R I of the formula III adjacent to N)/((integral of all of the C atoms of R I of the formula III adjacent to N)+(integral of all of the C atoms of R I of the formula I adjacent to N)).
  • the product produced by the process according to the invention can comprise compounds of the general formula IV, V and/or VI R 3 —X 1 —C(O)—NH—NH—C(O)—X 1 —R 4 (IV), (R 1 ) 3-a (R 2 ) a Si—R I —NH—C(O)—NH—NH—C(O)—NH—R I —Si(R 1 ) 3-a (R 2 ) a (V), (R 1 ) 3-a (R 2 ) a Si—R I —NH—CO—NH—NH—CO—X 1 —R 3 (VI).
  • the silicon-containing azodicarbamides of the general formula I can be used as coupling agents between inorganic materials, e.g. glass beads, glass fragments, glass surfaces, glass fibres, or oxidic fillers, preferably silicas, e.g. precipitated silicas and fumed silicas,
  • thermosets e.g. thermosets, thermoplastics or elastomers, or, respectively, as crosslinking agents and surface-modifiers for oxidic surfaces.
  • organic polymers e.g. thermosets, thermoplastics or elastomers, or, respectively, as crosslinking agents and surface-modifiers for oxidic surfaces.
  • the silicon-containing azodicarbamides of the general formula I can be used as coupling reagents in filled rubber mixtures, e.g. tyre treads, technical rubber items or shoe soles.
  • An advantage of the process according to the invention is that it is possible to produce silicon-containing azodicarbamides of the general formula I in a single synthetic step from synthetic units familiar in industry.
  • Another advantage of the process according to the invention is that there is no requirement for the oxidation of hydrazine derivatives, and high yields are achieved, as also are high purities.
  • Another advantage of the process according to the invention is that there is no requirement for any complicated purification of the products obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US13/580,780 2010-03-29 2011-03-11 Process for preparing silicon-containing azodicarbamides Active 2031-05-14 US8664370B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102010003387A DE102010003387A1 (de) 2010-03-29 2010-03-29 Verfahren zur Herstellung von siliciumhaltigen Azodicarbamiden
DE102010003387.1 2010-03-29
DE102010003387 2010-03-29
PCT/EP2011/053824 WO2011120792A1 (de) 2010-03-29 2011-03-15 Verfahren zur herstellung von siliciumhaltigen azodicarbamiden

Publications (2)

Publication Number Publication Date
US20130012691A1 US20130012691A1 (en) 2013-01-10
US8664370B2 true US8664370B2 (en) 2014-03-04

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Country Status (16)

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US (1) US8664370B2 (de)
EP (1) EP2552925B1 (de)
JP (1) JP5744173B2 (de)
KR (1) KR101761965B1 (de)
CN (1) CN102822183B (de)
BR (1) BR112012024805B1 (de)
CA (1) CA2794944C (de)
DE (1) DE102010003387A1 (de)
ES (1) ES2505498T3 (de)
MX (1) MX2012010262A (de)
MY (1) MY156704A (de)
PL (1) PL2552925T3 (de)
RU (1) RU2559876C2 (de)
UA (1) UA105843C2 (de)
WO (1) WO2011120792A1 (de)
ZA (1) ZA201207291B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9981995B2 (en) 2014-04-22 2018-05-29 Evonik Degussa Gmbh Azocarbonyl-functionalized silanes

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2444782T3 (es) 2011-04-01 2014-02-26 Evonik Degussa Gmbh Mixturas de caucho
US8741994B1 (en) * 2012-12-13 2014-06-03 Toyo Tire & Rubber Co., Ltd. Alkoxysilyl group-containing azo compound and rubber composition using the same
TWI591848B (zh) * 2013-11-28 2017-07-11 晶元光電股份有限公司 發光元件及其製造方法
FR3020066B1 (fr) 2014-04-22 2016-04-01 Michelin & Cie Composition de caoutchouc pour pneumatique comportant un agent de couplage azosilane
EP3181571B1 (de) * 2015-12-17 2019-07-24 Evonik Degussa GmbH Silizium-enthaltende azodicarboxamide, deren herstellung und verwendung

Citations (5)

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Publication number Priority date Publication date Assignee Title
DE2704506A1 (de) 1976-02-06 1977-08-11 Malaysian Rubber Producers Substituierte azosilane, verfahren zu ihrer herstellung und ihre verwendung
US20090186961A1 (en) 2005-05-26 2009-07-23 Michelin Recherche Et Technique S.A. Rubber Composition for Tire Comprising an Organosilicon Coupling Agent and an Inorganic Filler Covering Agent
US20090221751A1 (en) 2006-01-28 2009-09-03 Evonik Degussa Gmbh Rubber Mixtures
US20090234066A1 (en) 2005-05-26 2009-09-17 Jose Carlos Araujo Da Silva Rubber composition for tire comprising an organosilicon coupling system
US7777063B2 (en) 2005-08-17 2010-08-17 Evonik Degussa Gmbh Organosilicon compounds their preparation and their use

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US3171851A (en) 1961-12-06 1965-03-02 Union Carbide Corp Amino methylphenyl silicon compounds
JP2787343B2 (ja) * 1989-09-08 1998-08-13 大塚化学株式会社 アゾ化合物
JP2510345B2 (ja) * 1990-08-30 1996-06-26 積水化学工業株式会社 アルコキシシリル基含有アゾ化合物及びその製造方法
FR2886294B1 (fr) * 2005-05-26 2007-07-20 Rhodia Chimie Sa Procede de preparation de composes organosiliciques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2704506A1 (de) 1976-02-06 1977-08-11 Malaysian Rubber Producers Substituierte azosilane, verfahren zu ihrer herstellung und ihre verwendung
US4118367A (en) 1976-02-06 1978-10-03 The Malaysian Rubber Producers Research Association Reinforced rubber
US20090186961A1 (en) 2005-05-26 2009-07-23 Michelin Recherche Et Technique S.A. Rubber Composition for Tire Comprising an Organosilicon Coupling Agent and an Inorganic Filler Covering Agent
US20090234066A1 (en) 2005-05-26 2009-09-17 Jose Carlos Araujo Da Silva Rubber composition for tire comprising an organosilicon coupling system
US7777063B2 (en) 2005-08-17 2010-08-17 Evonik Degussa Gmbh Organosilicon compounds their preparation and their use
US20090221751A1 (en) 2006-01-28 2009-09-03 Evonik Degussa Gmbh Rubber Mixtures

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
International Report on Patentability and Written Opinion received in PCT/EP2011/053824, issued Oct. 2, 2012.
International Search Report received in PCT/EP2011/053824, mailed Jun. 28, 2011.
Written Opinion received in PCT/EP2011/053824, mailed Jun. 28, 2011.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9981995B2 (en) 2014-04-22 2018-05-29 Evonik Degussa Gmbh Azocarbonyl-functionalized silanes

Also Published As

Publication number Publication date
EP2552925A1 (de) 2013-02-06
WO2011120792A1 (de) 2011-10-06
RU2012145738A (ru) 2014-05-10
ZA201207291B (en) 2013-06-26
BR112012024805B1 (pt) 2018-05-15
US20130012691A1 (en) 2013-01-10
JP5744173B2 (ja) 2015-07-01
CA2794944C (en) 2017-05-09
CN102822183A (zh) 2012-12-12
MX2012010262A (es) 2012-11-23
EP2552925B1 (de) 2014-07-23
ES2505498T3 (es) 2014-10-10
KR101761965B1 (ko) 2017-07-26
JP2013523671A (ja) 2013-06-17
DE102010003387A1 (de) 2011-09-29
KR20130034014A (ko) 2013-04-04
UA105843C2 (uk) 2014-06-25
MY156704A (en) 2016-03-15
PL2552925T3 (pl) 2014-12-31
CN102822183B (zh) 2015-11-25
CA2794944A1 (en) 2011-10-06
RU2559876C2 (ru) 2015-08-20
BR112012024805A2 (pt) 2016-06-07

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